HU204830B - Herbicidal compositions comprising sulfonamide derivatives and process for producing the active ingredients - Google Patents

Abstract

Sulphonamides of the general formula I <IMAGE> in which the substituents and indices have the following meanings: R<1> represents hydrogen or C1-C4-alkyl, R<2> represents hydrogen, optionally substituted C1-C6-alkyl; C3-C4-alkenyl; C3-C4-alkynyl or optionally substituted saturated or monounsaturated 5- to 7-membered heteroaryl; R<3> and R<4> represent halogen; optionally substituted C1-C4-alkoxy, C1-C4- alkylthio, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkenylthio, C2-C6- alkynyl, C2-C6-alkynyloxy, C2-C6-alkynylthio, C3-C6-cycloalkyl, C3-C6- cycloalkylthio, C5-C6-cycloalkenyl, C3-C6-cycloalkoxy, C5-C6- cycloalkenyloxy, C5-C6-cycloalkenylthio, phenyl, phenoxy, phenylthio, benzyl, benzyloxy or benzylthio; the groups mentioned under R<2> or NR<7>R<8> in which R<7> and R<8> represent hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl, C5-C6-cycloalkenyl, optionally substituted phenyl and/or benzyl, or represent optionally substituted C4-C6-alkylene which can be interrupted by oxygen, sulphur or nitrogen; X represents nitrogen or =CR<5>- in which R<5> represents one of the radicals R<3>, n represents 0 or 1 and A represents optionally substituted aryl with one or two rings, containing one to two nitrogen, oxygen and/or sulphur atom(s), and their agriculturally useful salts, and herbicidal and plant- growth-regulating compositions containing them.

Description

The present invention relates to a process for the preparation of new sulfonamide derivatives of the formula (I) and to herbicides which contain these compounds as active ingredients. In the general formula (i)

R ¹ is hydrogen or C 1-4 alkyl;

R ² is hydrogen or balogen, C 1 -C 4 alkoxy optionally substituted with halo, or -NR ⁷ R ⁸ wherein

R ^{7 and} R ⁸ are C 1 -C 4 alkyl,

R ³ is hydrogen, halogen, or C 1 -C 4 alkoxy,

X is nitrogen or = CH, n is 0 or 1, and

A is optionally substituted with 1 to 3 halogens or halogen, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, and Phenyl substituted with up to two groups selected from (C 1 -C 4 alkoxy) (C 1 -C 4 alkoxy) optionally thienxyl optionally substituted by halogen or (C 1 -C 4) alkoxycarbonyl, further naphthyl or quinolyl.

The invention also relates to a process for the preparation of the compounds of the formula I and their agriculturally acceptable salts.

Herbicidal sulfonamide derivatives are known from EP-A-150974, but their effect on selectivity and specificity is lagging behind. The known compounds contain a triazolyl fused pyridyl ring and the two rings are attached by a common nitrogen atom.

The aim of our work leading to the development of the present invention was to provide compounds with satisfactory performance in all respects. Our task was solved by the preparation of new sulfonamide derivatives of formula (I). We have also developed herbicidal compositions containing the compounds of formula I and their agriculturally acceptable salts as active ingredients.

Compounds of formula (I) may be prepared by analogous procedures to known procedures (a) to (e).

(a) Procedure

The compounds of formula (I) are known in the art according to JMed. Chem., 9, 373 (1966)] may be prepared by reacting a sulfonamide derivative of formula (Π) with a halogenated heteroaryl derivative of formula (Π3) in an inert organic solvent in the presence of a base. Hal of formula (ED) is a balogen atom (e.g., fluorine, chlorine, bromine or iodine); preferably the use of compounds of formula (ΙΠ) wherein Hal is a chlorine craving bromine atom.

The reaction solvent is suitably a halogenated hydrocarbon (e.g., tetrachloroethane, methylene dichloride, chloroform, dichloroethane, chlorobenzene or 1,2-dichlorobenzene), an ether (e.g., diethyl ether, methyl tert-butyl ether). , ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane), a dipolar aprotic solvent (e.g. acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, 1,3-dimethyltetrahydro-2 (1 H) -pyrimidinone or 1,3-dimethylimidazolidin-2-one), an aromatic hydrocarbon (e.g., benzene, toluene, xylene, pyridine or quinoline), a clone (e.g., acetone or methylethylketone), an alcohol (e.g., methanol, ethnol, isopropanol or tert-butanol) or a mixture thereof.

The reaction may be carried out at a temperature ranging from 25 ° C to the boiling point of the solvent or solvent mixture used.

The basic catalytic activity of the reaction is basic aromatic nitrogen compounds (pyridine, 4- (dimethylamino) pyridine or quinoline), tertiary aliphatic amines (e.g. triethylamine, N-ethyldiisopropylamine or N-methylmorpholine), bi- or tricyldic amines. [e.g., diazabicyclo-undecene (DBU) or diazabicyclooctane (DABCO)] as well as hydroxides, hydrides, alkoxides, carbonates or bicarbonates of alkali or alkaline earth metals, especially sodium or potassium hydroxide, or lithium hydride, sodium methylate or ethylate, potassium tert-butylate, sodium or potassium carbonate or sodium or potassium bicarbonate. If necessary, mixtures of the above bases may also be used.

In the reaction mixture, the molar ratio of the reacting sulfomide (Π) to the heteroaryl halide (ΙΠ) can range from 1: 1 to 1: 3, while the molar ratio of the catalytic base to the sulfonamide (Π) is also 1: 1. It can be 1: 3. The concentration of the starting compounds in the solvent is generally from 0.1 to 5 mol / l, preferably from 0.2 to 2 mol / l.

The reaction is particularly preferred in a dipolar aprotic solvent (e.g., acetonitrile, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, 1,3-dimethyl-tetrahydro-2 (1H) -pyrimidinone or 1,3-dimethylimidazolidine-2- on) or in an ether (e.g., ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane) at a temperature of 80-150 ° C, sodium hydride, methylate or ethylate, or potassium tert-butylate, such as base in the presence of. More preferably, the sulfonamide of formula (Π) is first converted to its corresponding salt with the appropriate base and then reacted with the halogenated heteroaryl derivative of formula (ΠΓ). The sulfonamide salt may be isolated but is not required; it is convenient to react the salt in situ in the same reaction mixture with the compound of formula (ΠΙ).

In many cases, the sulfonamide derivatives of the general formula (H) are commercially available. The new derivatives can be prepared by known methods (Pawlenko, Houben-Weyl, Methoden derorganchen Chemie, E / 11, (Organic Sulfur Compounds), G. Thieme Verlag, Stuttgart (1985), p. 1098).

HU 204,830 Β

The halogenated heteroaryl compounds of formula (IH) may also be prepared by known methods or analogs thereof (Shaw, Comprehensive Heterocyclic Chemistry, Vol. 5,1). Ed. (1984), Chapter 4.09, page 499; Montgomery and Secrist, Comprehensive Heterocyclic Chemistry, Vol. Ed. (1984), Chapters 4.10, 615 and 635; Lister, The Chemistry of Heterocyclic Compounds, Fused Pyrimidines (1971) and Robins, Heterocyclic Compounds, Vol. 8,162. (1967).

(b) procedure

Compounds of formula (I) wherein R ¹ is other than hydrogen may be prepared by a known method, in the presence of a base, of a sulfonyl halide of formula (TV) in the presence of a base of a heteroaryl of formula (V). with an amine derivative where R ^{1 is} other than hydrogen. In the formula (IV), Hal represents a halogen atom, for example fluorine, chlorine or bromine, especially chlorine.

The reaction is essentially carried out in the solvents or mixtures thereof described in Process A, in the presence of the bases listed therein, at a temperature between 25 ° C and the boiling point of the solvent. When a basic compound such as pyridine is selected as solvent, the presence of an auxiliary base is unnecessary.

In the reaction mixture, the molar ratio of the heteroarylamine derivative of formula (V) to the catalytic base may be 1: 1 to 1: 3. However, the sulfonyl halides of the formula (IV) and the reaction accelerating base may be used in smaller amounts than the equivalent. The concentration of the starting compounds in the solvent is generally from 0.1 to 5 mol / l, preferably 0.22 mol / l.

The sulfonyl halides of formula (IV) are either commercially available or may be prepared by methods well known in the art (Clarke et al., Org. Synth. Coll. Vol. I, 2nd edition, p. 85 (1941); Hoffmann, Org. Synth. ., Vol. 60,121). The heteroaryl amines of formula (V) may also be prepared by methods well known in the art, and are summarized in literature A on the preparation of heteroaryl halides of formula (ΕΠ).

c) procedure

For example, compounds of formula (I) may be prepared by synthesizing a sulfonyl isocyanide derivative of formula (VI) in a known manner (Synthesis, 1982, 11, 984; Chem. Bér., 99,2885 (1966)], with a diamino-heteroaryl derivative of formula (VHa) or (VHb), optionally in the presence of a base. In formula (VI), Z represents a halogen atom (e.g., chlorine or bromine); it is preferred that u is chlorine.

The reaction solvent may be one of the chlorinated hydrocarbons, ethers, aromatic or dipolar aprotic solvents listed in process (a), or mixtures thereof; the temperature may range from 25 ° C to the boiling point of the solvent.

Particularly preferred is the reaction in a halogenated hydrocarbon (e.g., chlorobenzene or 1,2-dichlorobenzene), an aromatic hydrocarbon (e.g., toluene or xylene), an ether (e.g., ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or dioxane), or in a dipolar aprotic solvent (e.g. acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, Nmethylpyrrolidone, 1,3-dimethyltetrahydro-2 (1H) pyridinone or 1,3-dimethylimidazolidin-2-one) ), At a temperature of 80-150 ° C. In the reaction mixture, the molar ratio of the reaction partners of formula (VI) and (VHa) or (VHb) is from 1: 1 to 1: 5, and the concentration of the starting compounds can be 0.1-5 mol / l, preferably 0.2-2 mol / l.

For compounds of formula VI wherein Z is halogen, it is preferable to carry out the reaction in the presence of at least 2 molar equivalents of the base to form the resulting hydrogen halide. The base is aromatic nitrogen compounds (pyridine, '4-dimethylamino-pyridine or coniline), tertiary aliphatic amines (triethylamine, N-ethyl-N-diisopropylamine or N-methylmorpholine)' bi- or tricyclic amines. (DBU or DABCO) or, more preferably, diamino heteroaryl derivatives of formula (VHa) or (VHb) may be used.

Compounds of formula VI can be prepared by known methods (Kühler; Houben-Weyl, Methoden derorganchen Chemie, Vol. E4, Carbonic Derivatives, G. Thieme Verlag, Stuttgart (1983), pp. 540 and 580) as well as VHa) or VHb [J. Brown, Coprehensive Heterocyclic Chemistry, Vol. 3 ,, i. Ed., 1984, Chapter 2.13, p. Jones, Comprehensive Heterocyclic Chemsitry, Vol.2, 1st Edition (1984), Chapter 2.08, p. 395].

(d) procedure

Compounds of formula I wherein R ² is C 1 -C 4 alkoxy or -NR 1 R ⁸ and / or R ^{3 is C} 1 -C 4 alkoxy and X is N are particularly preferably prepared by: a sulfonamide derivative of formula (Xla) or of formula Xlb - wherein Hal represents a halogen atom such as fluorine, chlorine or bromine, especially chlorine, and in the case of compounds of formula Xlb R ² is other than halogen, in an organic solvent in the presence of base -C alcoholate or a NHR ⁷ R ⁸ amine derivative.

The reaction may be carried out essentially in the solvents and bases listed in process (a) or combinations thereof. The molar ratio of the reagent NHR ⁷ R ^{8 to} the sulfonamide of formula XI * or Xlb may be 1: 1-5: 1, preferably 3: 1-5: 1. Solvents include alcohol (e.g. methanol, ethanol, propanol, isopropanol, butanol, isobutanol or tert-butanol), ether (e.g., diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane) or dipolar solvents (e.g. acetonitrile, dimethylformamide3)

EN 204830 ót or dimethylsulfoxide); the reaction temperature may range from room temperature to 130 ° C

(e) procedure

This process is a variant of process d) for the preparation of compounds of formula Q wherein R ² and R ^{3 are each C} 1 -C 4 alkoxy and X is nitrogen. The corresponding sulfonamide derivative of formula Xlc in an organic solvent, in the presence of a base with 14 carbon atoms of the alcohol Hal of fluorine, chlorine or bromine, especially chlorine.

The process may be carried out in general and in particular in the manner and under the conditions described in process d).

Particularly preferred are the sulfonamide derivatives of the formula I in which they are present

R ^{1 is} hydrogen or methyl, with the proviso that when R ^{1 is} hydrogen, the tautomers which may be present (i.e., that the hydrogen atom is a 7 or 9 nitrogen bond) are not distinguished;

R ^{2 and} R ^{3 are} hydrogen, fluoro or chloro, or methoxy, ethoxy, propoxy, 1-methyl-ethoxy and R ² may also be trifluoromethoxy or Ν, Ν-dimethylamino;

The phenyl, naphthyl, quinolyl or thienyl group and the phenyl group may be substituted one to three times with fluorine or chlorine, or with 1-2 ethyl, propyl, isopropyl, trifluoromethyl, methoxy, ethoxy, methylethoxy, tert-butoxy, trifluoromethoxy, trifluoroethoxy, dodoethoxy, methoxyethoxy, ethoxyethoxy, methoxycarbonyl or ethoxycarbonyl, and the compounds thereof.

Compounds of formula (I) are illustrated in more detail by formulas (Ja), (Ib), (Ic) and (Id); the symbols are as given above

When A is substituted phenyl, it is preferably one to three halogens or one alkoxycarbonyl group or one halogen atom and one alkyl or alkoxy group or one or two alkyl or alkoxy groups, one haloalkyl or haloalkoxy or alkoxyalkoxy group. group of drinks replaced.

The herbicidal compositions containing the compounds of formula (I) as active ingredients may be formulated as solutions, dusts and suspensions for immediate use, but may be formulated as high-activity water-in-oil or other solvent-based suspensions or dispersions, emulsions, oily dispersions, ointments, or granules thereof. These formulations may be applied by spraying, fogging, dusting, spraying or irrigating. The form of the preparation will in each case be suitably selected for the intended purpose (such as will provide the finest distribution of the active ingredient within the given conditions).

The compounds of formula (I) are generally suitable for the preparation of directly applicable formulations, solutions, emulsions, ointments or oily dispersants. For their preparation, medium or high boiling petroleum fractions (e.g. kerosene or gas oil) as well as tar oils, vegetable or animal oils, aliphatic, cyclic or aromatic hydrocarbons (e.g., toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene) are used as carriers. and methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, or highly polar solvents (e.g., dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone) or water.

Aqueous application forms can be prepared from emulsion concentrates, ointments, wettable powders or water dispersible granules by adding the required amount of water. For the preparation of emulsions, ointments or oil dispersions, the herbicide is homogenized, either alone or first, in water or in solution in an oil or solvent, with wetting, tackifying, dispersing or emulsifying agents. However, formulations containing the active compounds and wetting, tackifying, dispersing or emulsifying agents may also be formulated, if necessary, and may be diluted with water.

The surfactants that can be used in the compositions are the alkali metal, alkaline earth metal or ammonium salts of aromatic sulfonic acids (lignin, phenol, naphthalim or dibutylnaphthalenesulfonic acid), and fatty acids, alkyl and alkylaryl sulfonates, alkyl, lauryl ether and fatty acids , sulphated salts of hexa-, hepta- and octadecanolenes, fatty alcohol glycol ethers, sulphonated naphthalene and its derivatives in the formaldehyde condenser, naphthalenes and their sulphonic acids in the condenser with phenol and formaldehyde, poly (oxyethylene) -, octyl and nonyl phenols, alkylphenyl and tributylphenyl poly (glycol ether), alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene ) alkyl ethers or poly (oxypropylene), lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulphite base or methyl cellulose.

Dusts, dusts, or blasting agents may be prepared by mixing the active ingredient with one or more solid carriers. Granules (in the form of pellets, impregnated or homogeneous) can be prepared by bonding the active ingredients to a solid carrier. Solid carriers include various minerals such as silica, silica gel, silicates, talc, kaolin, limestone, lime, chalk, material, loess, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea) and vegetable materials (flour, sawdust, bark and walnut flour, cellulose powder, etc.) and any other solid material.

The active ingredient content of the compositions may generally be from 0.195% by weight, preferably from 0.5% to 90% by weight, of the compounds of the present invention.

Examples of formulations that can be prepared are described below.

Example 1

Preparation of formulated preparations

a) 90 parts by weight of 1.005 are mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. The resulting solution is suitable for application in small drops.

b) 20 parts by weight of 1.006 are dissolved in a mixture consisting of 80 parts by weight of xylene, 5 parts by weight of calcium didexylbenzene sulphonate, 10 parts by weight of dispersant A and 5 parts by weight of dispersant A (8-10 mol of ethylene oxide). and the reaction product of 1 mol of N-monoethanolamine oleate (40 mol of ethylene oxide and 1 mol of castor oil). The solution is mixed with 100,000 parts by weight of water to give a finely divided dispersion having an active ingredient content of 0.02% by weight.

c) 20 parts by weight of 1.007 are dissolved in a mixture of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of dispersant (C) and 10 parts by weight of dispersant (B) (dispersant (C) is 7 moles ethylene oxide and 1 mole the reaction product). The solution is mixed with 100,000 parts by weight of water to give a finely divided dispersion having an active ingredient content of 0.02% by weight.

d) 20 parts by weight of compound 1.008 are dissolved in a mixture of 25 parts by weight of cyclohexanone, 65 parts by weight of petroleum derivatives (b.p. 210-280 ° C) and 10 parts by weight of dispersant B). The solution is mixed with 100,000 parts by weight of water to give a finely divided dispersion having an active ingredient content of 0.02% by weight.

e) 20 parts by weight of 1.009 are thoroughly mixed with 3 parts by weight of diisobutylnaphthalene-alpha-sulphonic acid sodium salt, 17 parts by weight of lignin sulphonic acid sodium salt (from sulphite slurry) and 60 parts by weight of a powdered silica gel. The composition is mixed with 20000 parts by weight of water to give a spray solution containing 0.1% by weight of active ingredient.

f) 3 parts by weight of compound 1.010 are thoroughly mixed with 97 parts by weight of fine kaolin. The resulting powder contains 3% by weight of active ingredient.

g) 30 parts by weight of Compound 1.011 are mixed with a carrier consisting of 92 parts by weight of pos-shaped silica gel and 8 parts by weight of paraffin oil sprayed on its surface. The resulting composition has a very good adhesion.

h) 20 parts by weight of compound 1001 are mixed with 2 parts by weight of calcium dodecylbenzene sulphonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of phenolsulphonic acid urea-formaldehyde condensate (sodium salt) and 68 parts by weight of paraffin oil. The composition thus obtained is a stable oily dispersion.

The formulations may be applied prior to emergence (pre-emergence) or after emergence (post-emergence). If the active ingredient also damages the crop, one of the selective application methods may be used, which is to control the sprayer so that the crop is as light as possible but covering the weeds underneath and the soil surface.

The amount of active ingredient used depends on the season, the species of the target plant and the stage of development, but in general it can be from 0.001 to 3 kg / ha, preferably from 0.01 to 1.0 kg / ha.

Due to the versatility of the application techniques, the compounds of the present invention and the herbicidal compositions containing them can be used to control weeds in a wide variety of crops.

The compounds of formula (I) can be used to influence plants at virtually any stage of development and are therefore useful as growth regulators.

The broadening and enhancement of the activity spectrum can be achieved when the compounds of formula (I) are used in admixture with known herbicides or growth regulators. Examples of active compounds that can be used in the compositions include diazines, 4H-3,1-benzoxazine derivatives, benzothiazolidinone, 2,6-dinitroaniline, N-phenylcarbamates, thiolcarbamates, halogenated carboxylic acids, triazines, amides, urea, diphenyl ether derivatives, triazinone, uracil or benzofuran derivatives, triazinone, uracil or benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinoline derivatives, carboxylic acids, aryloxy or (heteroaryl) oxypropionic acids, and the salts, esters or amides of the foregoing, as well as any other active ingredient.

A further advantageous effect can be achieved by combining the compounds of the formula I or other herbicides with other pesticides, such as insecticides, fungicides or antibacterial agents. Mixing with mineral salt and nutrient solutions to eliminate nutritional deficiencies in plants is also important. The compounds may also be mixed with non-phytotoxic oils or oily concentrates.

The following examples illustrate the preparation of compounds of formula I from the corresponding starting compounds and the physical properties of the compounds prepared.

Example 2

Preparation of N ¹ - (2,6-Dichloro-7-methyl-8-purinyl) -benzenesulfonamide (process a, compound 1.001)

Sodium benzenesulfonamide (10.8 g, 50.0 mmol) was suspended in dimethylformamide (100 mL) and 2,6,8-trichloro-7-methylpurine (11.9 g, 50.0 mmol) was added at 60 ° C. The mixture was reacted at 80 ° C for 8 hours, then cooled to room temperature, poured into ice water, 10% w / w

After acidifying with 204830 Β of solution, the precipitate which is filtered is dried and dried. 11.7 g of colorless crystals are obtained; yield 65%.

¹ H-NMR (250MHz, d ⁶ -DMSO, ppm): 3.60 (s, 3H, N-CH ₃ ).

7.60 (mc, 3H, aryl-H)

7.95 (mc, 2H, aryl-H)

Example 3

Preparation of N ¹ - (2-Chloro-7-methyl-6-methoxy-8-purinyl) -benzenesulfonamide (d / Method 1.002)

Compound 1.001 (3.00 g, 8.00 mmol) (Example 1) was dissolved in methanol (50 mL) and sodium methylate (2.90 g, 16.0 mmol) was added as a 30% solution. The mixture was stirred for 12 hours at room temperature and concentrated in a rotary evaporator. The residue was stirred in water and acidified with dilute hydrochloric acid to give colorless crystals (2.30 g, 81%). 20 © -NMR (250MHz, d ⁶ -DMSO, ppm):

3.50 (s, 3H, N-CH ₃ )

4.05 (s, 3H, OCH ₃ )

7.55 (mc, 3H, aryl-H)

7.95 (mc, 2H, aryl-H)

Example 4

Preparation of N ¹ - (7-Methyl-2,6-dimethoxy-8-purinyl) -benzenesulfonamide (Preparation 1.003)

3.60 g (10.0 mmol) of compound 1.001 (Example 1)

Dissolve in 200 ml of methanol, add sodium methylate (5.40 g, 30.0 mmol) as a 30% w / w solution and react in an autoclave at 120 ° C for 12 hours. After cooling to room temperature, the mixture was concentrated in a rotary evaporator, the residue was stirred in water and acidified with 10% hydrochloric acid. 3.20 g of colorless crystals are obtained; yield 92%. 1 H-NMR (250MHz, d ⁶ -DMSO, ppm): 40

3.45 (s, 3H, N-CH ₃ ) 7.50 (mc, 3H, aryl-H)

3.90 (s, 3H, OCH ₃ ) 7.95 (mc, 2H, aryl-H)

4.05 (s, 3H, OCH ₃ )

Example 5

^{Preparation of} N ¹ - (2,6-Dichloro-7-methyl-8-purinyl) -2- (methoxycarbonyl) benzenesulfonamide (b / process 1.020)

8-Amino-2,6-dichloro-7-methyl-purine (3.00 g, 14 mmol) was dissolved in pyridine (150 mL) and then 2- (methoxycarbonyl) (6.60 g, 28.0 mmol) at 70 ° C. benzene sulphochloride is added. After 3 hours at 70-80 ° C, the reaction mixture was concentrated in a rotary evaporator, the residue was stirred in water and acidified with dilute hydrochloric acid. The desired compound in the form of bama powder was ¹ H-NMR (250MHz, d ⁶ -DMSO, ppm):

3.60 (s, 3H, N-CH ₃ ) 7.70 (mc, 2H, aryl-H)

3.80 (s, 3H, CO ₂ CH ₃ ) 8.10 (mc, 1H, aryl-H)

7.60 MC, 1H, Aryl-H)

Example 6

Preparation of N ¹ - (2,6-Dimethoxy-8-purinyl) -benzenesulfonamide (c / Method 1.004) in 4,5 ml of 4,5-diamino-2,6-dimethoxy-dioxane (2.20 g, 13.0 mmol) in dioxane To a mixture of pyrimidine and 2.60 g (26.0 mmol) of triethylamine, 3.00 g (13.0 mmol) of benzenesulfonyl isocyanide dichloride are slowly added dropwise at room temperature, with stirring at 100 ° C. hours. After cooling, the mixture is filtered, the filtrate is concentrated in a rotary evaporator and the residue is crystallized from methylene chloride / methyl tert-butyl ether.

© -NMR (250MHz, d ⁶ -DMSO, ppm):

3.90 (s, 3H, OCH ₃ )

4.00 (s, 3H, OCH ₃ )

7.55 (mc, 3H, aryl-H)

7.95 (mc, 2H, aryl-H)

Examples 1-3 were prepared analogously to those described in the examples above. Compounds listed in Tables 1 to 4.

Table 1 Compounds of formula (Ia)

Row-

song THE R ¹ R ² r ^{3 1} HNMR [d ⁶ DMSO, δ (ppm)]; Op ['C] 1001 phenyl ch ₃ the the 3.60 (s, 3H), 7.60 (mc, 3H), 7.95 (mc, 2H); 1002 phenyl ch ₃ and ₃ cl 3.50 (s, 3H), 4.05 (s, 3H), 7.55 (mc, 3H), 7.95 (mc, 2H) 1003 phenyl ch ₃ and ₃ and ₃ 3.45 (s, 3H), 3.90 (s, 3H), 4:05 (s, 3H), 7.50 (m c, 3H); 7.95 (c, 2H); 1004 phenyl H and ₃ and ₃ 3.90 (s, 3H), 4.00 (s, 3H), 7.55 (mc, 3H), 7.95 (c, 2H); 1005 2-a-phenyl ch ₃ the the 3.60 (s, 3H), 7.50-7.60 (m, 3H), 8.15 (c, lH); 1006 2-phenyl ch ₃ and ₃ the 3.55 (s, 3H), 4.05 (s, 3H), 7.45-7.60 (m, 3H), 8.15 (c, lH); 1007 2-phenyl ch ₃ and ₃ and ₃ 3.50 (s, 3H), 3.90 (s, 3H), 4.05 (s, 3H); 7.45-7.60 (m, 3H), 8.15 (c, lH); 1008 2,6-dichloro-phenyl ch ₃ the the 3.60 (s, 3H), 7.45-7.60 (m, 3H); 1009 2,6-dichlorophenyl ch ₃ and ₃ the 3.55 (s, 3H), 4.10 (s, 3H), 7.50-7.65 (m, 3H)

HU 204 830 B

Continuation of Table 1 Compounds of Formula Ia

Serial number AR ¹ R ² R ^{3 and} HNMR [d ⁶ DMSO, δ (ppm)]; Mp [° C]

1010 2,6-dichlorophenyl CH ₃ and ₃ and ₃ 1.01 i 2,6-dichloro- phenyl ch ₃ N (CH ₃ ) ₂ cl 1012 2,5-dichlorophenyl ch ₃ cl cl 1013 2,5-dichloro- phenyl ch ₃ OCH ₃ cl 1014 2,5-dichlorophenyl ch ₃ and ₃ and ₃ 1015 3-F-Ph ch ₃ cl cl 1016 3-F-Ph ch ₃ and ₃ cl 1017 3-F-Ph ch ₃ and ₃ and ₃ 1018 4-F-Ph ch ₃ cl cl 1019 4-F-phenyl ch. OCH ₃ cl 1020 2-CO ₂ CH ₃ -phenyl ch ₃ cl cl 1021 2-Cl, 6-CH ₃ -phenyl ch ₃ cl cl 1022 2-a, 6-CH ₃ -phenyl ch ₃ and ₃ cl 1023 2-Cl, 6-CH ₃ -phenyl ch ₃ and ₃ and ₃ 1024 2-OCH ₃ -phenyl ch ₃ cl cl 1025 2-OCH ₃ -phenyl ch ₃ and ₃ cl 1026 2-OCH ₃ -phenyl ch ₃ and ₃ and ₃ 1027 2-OCH ₃ -phenyl ch ₃ N (CH ₃ ) ₂ cl 1028 4-QCH ₃ -femi CH ₃ - and ₃ and ₃ 1029 2-naphthyl ch ₃ cl cl 1030 2-naphthyl ch ₃ and ₃ cl 1031 2-naphthyl ch ₃ and ₃ and ₃ 1031 2-naphthyl ch ₃ qch ₃ and ₃ 1032 1-naphthyl ch ₃ cl cl 1033 1-naphthyl ch ₃ and ₃ cl

1034 1-naphthyl CH ₃ and ₃ and ₃ 1035 8-quinolyl ch ₃ cl cl 1.036 8-quinolyl ch ₃ OCH ₃ the 1037 2-thienyl CH cl cl 1038 2-thienyl ch ₃ OCH ₃ cl 1039 2-thienyl ch ₃ and ₃ and ₃ 1040 3-CI, 2-thienyl ch ₃ the cl

3.50 (s, 3H), 3.80 (s, 3H), 3.95 (s, 3H), 7,40-7.50 (m, 3H);

3.05 (s, 6H), 3.55 (s, 3H), 7.40-7.55 (m, 3H);

3.60 (s, 3H), 7.60 (mc, 2H), 8.20 (c, lH);

3.55 (s, 3H), 4.05 (s, 3H), 7.65 (mc, 2H), 8.20 (c, lH);

3.55 (s, 3H), 3.90 (s, 3H), 4.05 (s, 3H), 7.65 (c, 2H);

8.20 (c, lH);

3.65 (s, 3H), 7.40 (c, lH), 7.60 (c, lH), 7.80 (c, 2H);

3.50 (s, 3H), 4.10 (s, 3H), 7.40 (c, lH), 7.60 (c, lH);

7.80 (c, 2H);

3.50 (s, 3H), 3.90 (s, 3H), 4.00 (s, 3H), 7.40 (c, lH);

7.60 (mc, 1H); 7.80 (mc, 2H);

3.60 (s, 3H), 7.40 (mc, 2H), 8.05 (c, 2H);

3.50 (s, 3H), 4.05 (s, 3H), 7.30 (mc, 2H), 8.00 (c, 2H);

3.60 (s, 3H), 3.80 (s, 3H), 7.60 (c, lH), 7.70 (c, 2H);

8.10 (c, lH);

2.70 (s, 3H), 3.55 (s, 3H), 7.30-7.50 (m, 3H);

2.70 (s, 3H), 3.50 (s, 3H), 4.00 (s, 3H), 7.30-7.50 (m, 3H);

2.70 (s, 3H), 3.50 (s, 3H), 3.90 (s, 3H), 4.00 (s, 3H);

7.20-7.40 (m, 3H);

3.55 (s, 3H); 3.70 (s, 3H); 7.05 (t, 1H); 7.15 (d, 1H); 7.55 (t, 1H); 7.85 (d) , lH);

3.45 (s, 3H), 3.65 (s, 3H); 4, O5 (s, 3H), 7.05 (t, IH);

7.15 (d, lH), 7.55 (t, IH), 7.85 (d, lH);

3.45 (s, 3H), 3.60 (s, 3H), 3.90 (s, 3H), 4.05 (s, 3H);

7.00 (t, IH), 7.10 (d, lH), 7.50 (t, IH), 7.85 (d, lH);

3.00 (s, 6H), 3.45 (s, 3H), 3.60 (s, 3H), 7.05 (t, IH);

7.15 (d, lH), 7.55 (t, IH), 7.85 (d, lH);

3.50 (s, 3H), 3.80 (s, 3H), 3.90 (s, 3H), 4.00 (s, 3H);

6.95 (mc, 2H), 7.90 (c, 2H);

3.60 (s, 3H), 7.70 (mc, 2H), 7.90-8.15 (m, 4H), 8.65 (s, lH);

3.50 (s, 3H); 4.00 (s, 3H); 7.55 (mc, 2H); 7.90-8.15 (m, 4H); 8.65 (s, 1H);

3.50 (s, 3H), 3.85 (s, 3H), 3.95 (s, 3H), 7.60 (c, 2H);

3.50 (s, 3H), 3.85 (s, 3H), 3.95 (s, 3H), 7.60 (c, 2H);

7.90-8.10 (m, 4H), 8.60 (s, lH);

3.55 (s, 3H), 7.60-7.75 (m, 3H), 8.00 (c, lH), 8.15 (c, lH);

8.40 (c, lH); 8.80 (c, lH);

3.45 (s, 3H), 3.95 (s, 3H), 7.55-7.70 (m, 3H), 7.95 (c, lH);

7.95 (c, lH), 8.05 (c, lH);

8.20 (c, lH), 8.35 (c, lH); 8.85 (c, lH);

3.50 (s, 3H); 3.80 (s, 3H); 3.90 (s, 3H); 7.45-7.60 (m, 3H); 8.15 (mc, 1H);

3.50 (s, 3H), 7.65 (c, lH), 7.80 (c, lH); 8.30 (c, lH);

8.50 (c, lH); 8.55 (c, lH); 8.80 (c, lH);

3.40 (s, 3H), 4.10 (s, 3H), 7.55 (c, lH), 7.70 (c, lH);

8.20 (c, lH); 8.50 (mc, 2H), 8.70 (c, lH);

3.65 (s, 3H), 7.10 (c, lH), 7.75 (c, lH), 7.85 (c, lH);

3.55 (s, 3H), 4.05 (s, 3H), 7.10 (c, lH), 7.75 (c, 2H);

3.50 (s, 3H), 3.95 (s, 3H), 4.05 (s, 3H), 7.10 (c, lH);

7.80 (c, 2H);

3.70 (s, 3H), 7.10 (d, lH), 7.90 (d, lH);

HU 204830 Β

Table 1 continued Compounds of general formula (Ia)

Row- song THE R ¹ R ² R ^{3 1} HNMR [d ⁶ DMSO, δ (ppm)]; Op ['C] 1041 3-CI, 2-thienyl ch ₃ and ₃ cl 3.50 (s, 3H), 4.10 (s, 3H), 7.10 (d, lH), 7.90 (d, lH); 1042 3-Cl-2-thienyl ch ₃ and ₃ OCH ₃ 3.55 (s, 3H), 3.90 (s, 3H), 4.05 (s, 3H), 7.10 (d, lH); 1043 4-CO ₂ CH ₃ , 3-thienyl ch ₃ cl cl 7.85 (d, lH); 3.55 (s, 3H), 3.70, 8.35 (c, 2H); 1044 4 Ο02ίΗβ »3- thienyl ch ₃ OCH ₃ the 3.50 (s, 3H), 3.70 (s, 3H), 4.10 (s, 3H), 8.30 (c, 2H); 1045 4-CO ₂ CH ₃ , 3-thienyl ch ₃ and ₃ OCH ₃ 3:45 (s, 3H), 3.70 (s, 3H), 3.90 (s, 3H), 4.05 (s, 3H) 1046 2-chlorophenyl H and ₃ ch ₃ 8.30 (c, 2H); 2.48 (s, 3H), 34.0 (s, 3H), 7.51 (mc, 3H), 8.19 (d, lH); 1047 2-chlorophenyl H and ₃ and ₃ 12.50 (s, IH), 12.70 (s, IH); 3.90 (s, 3H), 4.05 (s, 3H), 7.51 (mc, 3H), 8.15 (d, lH); 1048 2-chlorophenyl ch ₃ F F 12.30 (s, IH); 12.60 (s, IH); 193 1049 2-phenyl-time ch ₃ OCH ₃ F 3.53 (s, 3H), 7.37 (mc, 2H), 7.63 (c, lH), 7.97 (c, lH) 1050 2,6-dichlorophenyl ch ₃ F F 13.0 (m, lH); 3.53 (s, 3H), 7.22 to 7.63 (m, 3H); 1051 2,6-dichlorophenyl ch ₃ OCH ₃ F 3.53 (s, 3H), 7.51 (c, lH), 7.60 (c, 2H); 1052 2,6-dichlorophenyl ch ₃ OCH ^ CE} cl 3.53 (s, 3H), 5.19 (q, 2H), 7.54 (m c, 3H); 1053 2,3-dichlorophenyl ch ₃ the the 244 1054 2,3-dichlorophenyl ch ₃ OCH, the 215 1055 2,4,5-metal ion ch ₃ the cl 255-227 1056 2-F-phenyl ch ₃ the cl 115-119 1057 2-F-phenyl ch ₃ and ₃ the 210-212 1058 2-F-phenyl ch ₃ F F 3.53 (s, 33H), 7.53 (me, IH), 7.64 (mc, 2H), 8.19 (d, lH); 1059 2,6-difluorophenyl ch ₃ cl cl 3.65 (s, 3H), 7.63 (c, lH), 8.05 (c, lH); 8.91 (c, lH); 1060 2,6-difluorophenyl ch ₃ and ₃ cl ♦ 3.61 (s, 3H), 4.15 (s, 3H), 6.91 (mc, 2H), 7.41 (c, 2H); 1061 2,6-difluorophenyl ch ₃ F F 167-169 1,062 2,6-difluorophenyl ch ₃ OCH ₃ F 3.56 (s, 3H), 4.08 (s, 3H), 7.23 (mc, 2H), 7.64 (c, 2H); 1,063 2-CO ₂ CH ₃ -phenyl ch ₃ OCH, cl 203-205 1,064 2-CH ₃ -phenyl ch ₃ cl cl 2.63 (s, 3H), 3.61 (s, 3H), 7.40 (mc, 3H), 8.07 (d, lH);

♦ spectrum in lor doroform-d solvent

Table 1 continued Compounds of general formula (fa)

Row- song THE R ¹ R ² R ^{3 1} HNMR [d ⁶ DMSO, δ (ppm)]; Op ['C] 1065 2-CH ₃ -em ch ₃ and ₃ the 2.61 (s, 3H), 3.49 (s, 3H), 4.03 (s, 3H), 7.39 (m c, 3H); 1066 2-CH ₃ -phenyl ch ₃ and ₃ OCH ₃ 8.05 (d, 1H), 0.87 (s, 1H); 2.63 (s, 3H), 3.50 (s, 3H), 3.89 (s, 3H), 4.01 (s, 3H); 1067 2 _i 5 "Gi3 ₁ CH3" phenyl ch ₃ cl the 7.38 (mc, 3H), 8.09 (d, lH); I2,45 (s, lH); 189-190 1068 2,5-CH ₃ , CH ₃ -phenyl ch ₃ and ₃ the 206-208 1069 Necrosis CH jCHy phenyl ch ₃ OCH, OCH, 182-184 1070 2-CF ₃ -phenyl ch ₃ cl cl 208-210 1071 2-CF ₃ -phenyl ch ₃ and ₃ cl 205-206 1072 2-CF, -phenyl CH OCH, OCH, 199-203 1073 2-O (CH 2) ₂ Cl-phenyl CH ₃ cl cl 115-119

HU 204,830 Β

Continuation of Table 1 Compounds of Formula Ia

Row- song AR ¹ R ² R ^{3 1} HNMR [d ^{6 in} DMSO, δ (ppm)]; Op fC] 1074 2-O (CH ₉ ) ₉ OCH, -phenU CH ₃ cl Cl 191-193 1075 2-O (GH ₂ ) ₂ OCH ₃ -phenyl ch ₃ OCH ₃ Cl 188 1076 2,5-OCH "OCH _r CH, cl cl 3.54 (s, 3H), 3.61 (s, 3H), 3.76 (s, 3H), 7, ll (s, 2H); phenyl 7.44 (s, lH), 12.85 (s, IH); 1077 2,5-OCH ₃ , OCH ₃ -CH ₃ and ₃ cl 3.46 (s, 3H), 3.61 (s, 3H), 3.76 (s, 3H), 4.04 (s, 3H); phenyl 7.07 (s, 3H), 7.44 (s, l, H), 12.62 (s, IH); 1078 2-OCH ₃ , 5-Br-phenyl CH ₃ cl cl 3.57 (s, 3H), 3.71 (s, 3H), 7.13 (c, lH), 7.73 (m c-H);

7.98 (c, lH);

Table 2 Compounds of formula (Ib)

number THE R ¹ R ² r5 ¹ HNMR [d ⁶ DMSO, δ (ppm)]; Op ['C] 2001 Cl 2,6-Cl-phenyl H CH ₃ cl α 3.60 (s, 3H), 4.70 (s, 2H), 7.40 (c, lH); 7.55 (c, 2H); 2002 Cl 2,6-Cl-phenyl H ch ₃ OCH ₃ cl 3:50 (s, 3H), 4:05 (s, 2H), 4.70 (s, 2H); 7:40 (c, lH), 7:55 (c, 2H) 2003 2-F-phenyl H CH ₃ cl cl 3.57 (s, 3H), 4.49 (s, 2H), 7.08-7.60 (m, 4H); 2004 2-F-phenyl H ch ₃ and ₃ cl 3.48 (s, 3H), 4.07 (s, 3H), 4.44 (s, 2H)

7.18 (mc, 2H); 7.35 (mc, 1H); 7.52 (mc, 1H);

Table 3 Compounds of Formula Ic

Serial number A R ¹ R ² R ^{a 1} HNMR [d ⁶ DMSO, δ (ppm); Op ['C] 3.001 phenyl H H H 7.15 (dd, lH), 7.55 (mc, 3H), 7.65 (dd, lH); 7.90 (mc, 2H), 8.05 (dd, lH);

Example 7

Application experiments

The herbicidal activity of the N-phenylsulfonamide derivatives of formula I is tested in greenhouse experiments.

For the pots, 300 ml plastic flower pots are used, in which 3% humus is made of clayey sandy soil. Plant seeds are sown to the depth required by the species.

For pre-emergence treatment, the spray solution of the active ingredient is applied directly to the soil surface. The spray is a water-based suspension or emulsion which is sprayed with a finely divided sprayer. After treatment, the culture pots are watered to allow the seeds to germinate and then covered with a transparent plastic lid until the seedlings appear. Coverage promotes uniform germination if not affected by experimental agents alone.

For postemergent treatment, the plants are first grown to a height of 3 to 15 cm, depending on the species, and then treated with an aqueous emulsion or suspension of the active ingredients. The plants are either seeded immediately or seeded in similar pots a few days before treatment. The applied dose is 0.5 kg active ingredient / ha.

The experimental plants are grown at the temperature required by the species (20-35 ° C for warm-demanding species, 10-25 ° C for cooler climate species) for 2-4 weeks. During the observation period, the plants are cared for in the usual manner and any symptoms attributable to the treatment are recorded.

Experiments are scored using a 0-100 extreme score system, where 0 is a healthy plant in all respects and 100 is a plant that has not emerged or is completely destroyed after hatching.

The experiments were carried out on the following plant species:

Latin name Hungarian name

Chemopodium album (CHEBL) lipatop

Chrysanthemum corinarium (CHYCO) Chrysanthemum Matricaria modora (MAIIN) Odorless Snapis alba (SINAL) White mustard

Zea mays (ZEAMX) corn

According to the results of the experiments, the compounds 1.001 and 1.057 produced according to the invention at a dose of 0.5 kg / ha, applied postemergently, showed very good activity against dicotyledonous weeds, while not damaging the crop (maize).

The results are shown in Tables 4 and 5.

The effect of the herbicide containing 1,009 arable compounds was compared with that of the herbicide containing the compound of formula A described as compound 10 of Table I of EP-A-150974. The assay was performed as described above.

The results are shown in Table 6. The data clearly show the superior effect of the herbicide according to the invention.

Table 4

Active ingredient Plant Damage ® Number ZEAMX CHYCO SINAL

1009 0 100 100 Table 5 Number of active ingredient % Damage to plants ZEAMX CHEAL MAIIN 1057 0 95 90

Table 5 continued

agent number % Damage to plants CHYCO SINAL 1057 100 98 Table 6 Plants Damage ® 1009 (THE) 1 0.5 1 0.5 kg / ha kg / ha kg / ha kg / ha Zeamays Stem plants: Amaranthus 0 0 0 0 retroflexus Galium 98 90 85 60 aparine Ipomoea 90 90 10 0 SPP Helianthus 65 60 40 20 annuus * 80 80 25 20

♦ ittgyom

Claims (2)

CLAIMS 1. An herbicidal composition comprising 0.1 to 95% by weight of the sulfonamide derivative of the formula R ¹ is hydrogen or C 1-4 alkyl; R ² is hydrogen or halo, C 1-4 alkoxy optionally substituted with halo, or -NR ⁷ R ⁸ wherein R ^{7 and} R ⁸ are C 1 -C 4 alkyl, R ³ is hydrogen, halogen, or C 1-4 alkoxy, X is nitrogen or = CH-, n is 0 or 1, and A is optionally substituted with 1 to 3 halogens or halogen, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 halo phenyl substituted with up to two groups selected from alkoxy and (C1-C4) alkoxy (C1-C4) -alkoxy, optionally substituted thienyl optionally with halogen or (C1-C4) -alkoxycarbonyl; solid and liquid carriers and diluents, preferably natural and artificial mineral grinds, aliphatic, aromatic and cyclic hydrocarbons, water, petroleum fraction, and surfactant additives, preferably 20 ionic and nonionic dispersants, emulsifiers and wetting agents together with at least one. Process for the preparation of the compounds of the formula φ and their salts -R ¹ , R ² , R ³ , X, A and n as claimed in claim 1, characterized in that 25 a) a sulfonamide derivative of formula Q wherein A and n are known in the art, in an inert organic solvent, in the presence of a base, with a halogenated heteroaryl derivative of formula ΠΙ 30 R ¹ , R ² and X have the meanings given in the scope, Hal is halogen, or b) for the preparation of compounds of formula φ in which R ¹ is C 1 -C 4 alkyl, R ² , R ³ , X, A and na are a sulfonyl halide of the general formula (TV) - wherein A and na are as defined Hal is a halogen atom represented by the formula: in a known inert organic solvent, in the presence of a base, with a heteroarylamine derivative of formula (V): wherein R ¹ and X are as defined herein, or c) a compound of Formula VI: wherein A and n are as defined herein, Z is halogen, in an inorganic organic compound; In a solvent 45, with a diamino heteroaryl derivative of the formula (VHa) or (VHb), wherein R ¹ , R ² and X are as defined herein, or (d) for the preparation of compounds of formula φ Wherein R ¹ , A and N ^{2 are as} defined above, R ^{2 is C} 1 -C 4 alkoxy or -NR ⁷ R ⁸ , X is N, R ^{3 is C} 1 -C 4 alkoxy, a compound of Formula Xla or Xlb a sulfonamide derivative, wherein the substituents are as defined herein, Hal is halogen, is reacted in a known organic solvent, in the presence of a base, with a C 1 -C 4 alcoholate or an R ^{7 and} R ⁸ amine of formula H ⁷ R ⁸ ; obsession HU 204,830 Β e) for the preparation of a compound of formula I wherein R ² and R 4 are the same C 1 -C 4 alkoxy, X is N, R ¹ , A and n are as defined above to give a sulfonamide derivative of formula XIc. - where A, n and R ^{1 are} as defined in the foregoing, Hal is halogen - is reacted in a known organic solvent with a C 1 -C 4 alcoholate in the presence of a base and, if desired, converted to its salt.